Complex formal lubricating composition



United States Patent COMPLEX COMPOSITION Alfred H. Matuszak,v Westfield,William E. McTurk, Elizabeth,-Delmer L.; C'o'ttle; Highland Park, andDavid W. Yung,.Westfield,.N. Ji,. assignors' toEsso ResearchandEngineeringv Companyga corporation of Delaware NoDra'wing;Application November 29, 1952, Serial No. 323,338

11 Claims; (Cl. 2 52-'42) This invention relates to syntheticlubricating compositions. Particularly the invention relates. tosynthetic lubricating compositions having outstanding lubricatingproperties at bothhighlaridlow temperatures and which have the advantageof. leaving. substantially no combustion chamber deposits in" thecylinders of. reciprocating engines. More particularly theinventionre'lates to new and improved synthetic lubricating oils whichcomprise the formals of, organic compounds: having at least one freehydroxyl group whiclfis' alcoholic in nature, and which contain= a-O['"CH2O(C1LH27LO)1/]ECH2-O linkage, x and'n'heing'i or more an'd'ybeing 1 or more.

In recent etforts to obtain superior lubricating compositions which haveunusual and: specific properties, there have been1develop'ed entirely"new synthetic materials with lubricating properties. In'. general" thesenew synthetic lubricants are characterized by viscosity properties thatare outstandingat both'l'o'w-a'nd high temperatures, especially whencompared to mineral oils. These outstanding low and high temperatureproperties are especially desirable for use in equipment designed tooperate over a grea't'ternperature difierential, such as jet engines foraircraft use, combustion engines for aircraft, and the like. It has beenfound" that mineral lubricating oils are generally undesirable for thelubricating of these engines because of their high and low temperatureviscosity limitations.

It'has also been found that synthetic lubricants may be desirable forthe lubricating of standard automotive en-. gines. In addition to theversatility of their vi'scosities, the use of some types of thesynthetic lubricants investigated havebeen found to result in very lowrates of combustion chamber deposit formation, particularly when'usedfor long periods of time. Low'rates of formation' of' combustion chamberdeposits result in increased power factor from fuel, less increase inthe octane requirement of the engine, less pre ignitio'n' tendency, anda general overall" improvement" in engine operation. These newlubricants'm'ay also serve to reduce or remove combustion chamberdeposits" from an engine already loaded with such deposits. 7

The'pre'sent invention relates to anew type ofsynthetic lubiicatingcomposition which comprises the formalis' of a wide range of organiccompounds which contain at least one free' hydroxyl group" and which isalcoholic in nature and which contains at least" three CH"2O"-"1inkages.7 p v It' has been'gene'rally accepted by the art that most acetals arenot of'sufiieie'nt stability to serve as lubri'cat ing compositions; lth'as'now beeri'foiind, however, and

forms the object'ofthis' invention, that the formals'of organic hydroxycompounds that" contain the linkage --O-'-[CH2 -O (CnHz'nO-l lrCH'z -Owhere x' and rt are 2. or more and y is lor more have excellentstability and have viscosity prop'erties that make them outstandinglubricating compositions;

A* generic fofmula for'the lubricating compositions of:

thisinventionsmay :he2writt'm asifol'lowsz "ice In the formula A and Brepresent the organic compounds less the hydroxyl group. x and nrepresent numbers having a value of 2 or more and y is 1 or more. Theradicals may be alike or different and may contain from 1 to 60 carbonatoms. A and B are selected such that the total number of carbon atomsin the formal is between about 20 and 130,. with compounds containingfromv about 25 to carbon atoms being preferred. The organic hydroxycompounds which serve as a source for the radicals A and B will bedefinedmore in detail below.

For use in reciprocating engines, particularly as a lubricant forautomotive engines, a lubricating composition must meet severalrequirements; In order to form an effective lubricating film and tomaintain that film at low and high temperatures it must have certainviscosity characteristics. At low temperatures thelubricant must besufiiciently labile to flow through: the circulatory system of theequipment and allowmovement of lubricated surfaces without an unduepower requirement. A lubricant having an ASTM pourpoint below about 35F. has suflicient low temperature l'ahilit'y to make it satisfactory inthese respects. for general. use. At high temperatures a lubricant musthay'e sufii'cient body or thickness to furnish and maintain a:satisfactory lubricating film. It has been found thata lubricant that issatisfactory in this respect willl have: a viscosity at 210 F. ofbetween about 2 to 60 centistokes, i. c. 32.8 and 280 Saybolt seconds,Universal; T e prevent undue lubricant loss, due to volatility" andgeneral molecular disintegration and to insure againstiexplosion hazardsat higher temperatures sometimesencounteredg a lubricating compositionshould have a flasli point in eXcess-of about 300 F. These requisitesare inherent in the term lubricating compositions, as used in. thisspecification, and the formals of this invention are limited to-thosewithin these operable ranges. The preferred materials, as contemplatedherein and as d'escr-ib'ed in the preferred embodiment hereof,-will=have'an.AST-1\'/l pour point below about 15"? F'., a flash pointabove about 375" F., and will have a viscosity within-the range of' 2.6to 13 centistokes, i. e., 35 to 70 Saybolt seconds, Universal, at 210 F.

In general it has been found that the above listed properties are afunction both of molecular structure and of molecular weight. This factmakes it possible, within certain limits, to prepare compositions havingsimilar low and high temperature properties in a variety of ways andalso enables the-manufacturer to tailor a composition to fit a certainsetof specifications within rather general limits. This fact alsoaccounts for the large number of organic materials containing alcoholichydroxyl groups available for preparing thecompositions of thisinvention.

In general the preparation of the complex formals of this invention isaccomplished by methods that require conventional techniques andmethods; Three general lines of approach may he followed.

1. The reactantsmay b'e adriibced in the reacting zone and heated toreflux temperature in the presence of an entraining agent such" as'hexane", heptane or the like. After recovery of the water of theory theproduct is washed free of any acidi'c ca'talysts and stripped free ofunreacted components.

2 A second approach is to adinixximoles of the glycol reactant with x1moles' ofiformaldehydeto obtain the central portion of the complex.formal, i. e'., the portion represented by H@'(CnH2'ho)Z| [@H2 O(E11.H2n())]:cH.

In another reacting zone equalmolesof an alcohol and" 3 to the alcoholhemiformal and heated to reflux temperature. The product, after removalof the theoretical water, is then washed and stripped as above.

3. In this third approach the hemiformal of the chosen alcohol is firstmade by heating equal moles of the alcohol and formaldehyde. Then tothis is added the desired molar proportion of a glycol and formaldehydeand the total mixture heated to reflux temperature to make the hydroxycomplex represented by Two moles of this material is then reacted withone mole of formaldehyde to obtain the product which is purified asabove.

The materials used to prepare these formals, that is organic hydroxycompounds containingat least one free hydroxyl group which is alcoholicin character, may be selected from the following partial list. Others,of course, may be used.

I. Unsubstituted alcohols Monohydric 1. Aliphatic (a) Methyl alcohol Eb)Ethyl alcohol Propyl alcohol (d) Isopropyl alcohol a n-Butyl alcoholIso-butyl alcohol Sec.-butyl alcohol 'I'ert.-butyl alcohol n-Amylalcohol Isoamyl alcohol n-Hexyl alcohol Iso-hexyl alcohol m)2-ethyl-1-butanol 2-ethyl-1-hexanol Octyl alcohol Iso-octyl alcohol2-octyl alcohol Iso-nonyl alcohol Decyl alcohol Lauryl alcoholTetradecyl alcohol Pentadecyl alcohol Octadecyl alcohol Allyl alcohol1;) Crotyl alcohol z) Oleyl alcohol cm) The terpineols bb) C3 to C2 Oxoalcohols 00) Alcohols derived from the Synol process dd) Alcoholsderived from the oxidation of petroleum fractions ee) Alcohols derivedfrom Guerbets reaction f7)1 frillcohols derived from the hydration of oe ns (go) Alcohols derived from the (hh) Mixtures of the above Aromatic(a) Benzyl alcohol b) Phenethyl alcohol (0) 3-phenyl-1-propanol (cl)a-Naphthyl carbinol (e) Cinnamyl alcohol (7) Diphenyl carbinol (g;Furfuryl alcohol (h Cnmic alcohol t) Vanillyl alcohol 1) Piperonylalcohol B. Polyhydric 1. Glycols M AAAAAAMAAAAMMAAAAMAAAA Oxyl synthesis1.2-propanediol 1.3-propnnediol 1,3-butanediol e) 1.4-butanediol f)1.5-pentanediol g) The various polyalkylene glycols, e. g.

1. Polyethylene glycols (a) Diethylene glycol 51;) Triethylene glycol c)Tetraethylene glycol 2. Polypropylene glycols (a) Dipropylene glycol (b)Tripropylene glycol sh) 1,2-cyclohexanedio1 i) Decanedi0l-1.10 2. Otherpolyhydric alcohols (11) Glycerol (b)2hydroxymethyl-2-methyl-propanedlol-I,3 (c) Pentaerythritol I v dorbitol e) Dipentaerythritol f) Dulcitol Trimethylol propane'letramethylol cyclohexanol t) Benzotrimethylol II. Substituted alcoholsMonohydric 1. Aliphatic (a) Halogenated alcohols 1. Ethylenechlorohydrin 2. Trlfluoro ethanol 3. Propylene chlorohydrln 4. Thevarious chloro-substltuted monoethers of polyalkylene glycolsEthanolamine 2-amino propanol 2-m'troethanol 2-nitropropanol2-nitrobutanol The various glycol monoesters, e. g. 1. Ethylene glycolmonoacetate 2. Propylene glycol monobutyrate Butylene glycol monolauratePolyethylene glycol monoesters Polypropylene glycol monoestersPolybutylene glycol monoesters he various glycol monoethers, e. g.

Ethylene glycol mono-methyl ether Propylene glycol mono-butyl etherButylene glycol mono-lauryl ether Polyethylene glycol mono-othersPolypropylene glycol mono-others Polybutylene glycol mono-ethersPolytrimethylene glycol mono-ethers (i) The various glycol mono-formals,e. g. the

mixed formals of glycols and alcohols (j) Hydroxy alkyl cyanides 1.Ethylene cyanohydrln 2. oz-Hyroxy lsobutyronltrile (k) Ethanolmorpholine 2. Aromatic (a) p-Methoxy benzyl alcohol (b) The variouschlorobenzyl alcohols (c) The various nitrobenzyl alcohols (11)2-anilino ethanol B. Polyhydric 1. Glycols (a) Halogenated glycols, e.g.

1. 3-chloro-1,2-propanediol 2. 2-chloro-1,3-propanediol (b)Nitroglycols, e. g.

1. 2-nitro-1,3-propaned1ol 2. 2-nitro-2methyl-propanediol-l,3 3.Trimethylol nitromethane (0) Amino glycols 1. 2-amino-1,3-propanediol 2.2-amino-2-methyl-1,3-propanediol 3. Diethanol amine 4. Trimethylolaminomethane C. Other hydroxy compounds 1. Esters of hydroxy acids (a)The varlous lactate esters (b) The various glycolate esters (c) Thevarious hydroxy stearate esters 2. Carbonyl substituted alcohols (41)Hydroxy ketones, e. g.

1. Hydroxy acetone (b) Hydroxy aldehydes, e. g.

1. a-Hydroxy adipaldehvde 2. B-Hydroxy propionaldehyde Particularlydesirable organic hydroxy compounds for use in this invention are thosehighly branched chain aliphatic alcohols prepared by the OX0 synthesis.This Oxo synthesis may be described as being the catalytic reaction ofan olefin with carbon monoxide and hydrogen. The reaction occurs attemperatures in the order of 300400 F., at pressures in the range ofabout 1000 to 3000 p. s. i., in the presence of a suitable catalyst,ordinarily a heavy metal carbonyl such as cobalt carbonyl. The resultingaldehyde is subsequently hydrogenated to a primary alcohol. This processis described in U. S. Patent No. 2,327,066 issued to Roelen in 1943.

In general the oxygenated group in a product from an olefin by the Oxoprocess is thought of as becoming attached to an unsaturated carbonwhich holds at least one hydrogen atom. In those cases Where the carbonmonoxide attacks a saturated carbon atom, it must be assumed either thatthat carbon has become unsaturated prior to reaction by a shift of ahydrogen atom or that the attack is directly on a carbon atom that istruly saturated. For example, Z-butene has been reported to e s s z egive l-pentanol and Z-methylbutanol in equal quantities,

hydrogen is attached to the unsaturated carbon atoms and the attack ofcarbon monoxide must either be on a rearranged olefin or on a saturatedcarbon atom.

It has been found that particularly desirable alcohols for the formationof the formals of this invention can be prepared by the application ofthe 0x0 synthesis to polymers and copolymers of C3 and C4 monoolefins.These monoolefins are. readily available in petroleum greener refinerystreams and processes for their conversion to liquid copolymers havebeen worked out by the art. One such process, known as U. 0. P.polymerization, consists of passing the olefin-containing stream inliquid phase in contact with an acid catalyst comprising phosphoric acidimpregnated on kieselguhr. Other acidic catalysts, such as phosphoricacid or copper phosphate impregnated on silica gel, sulfuric acid,Friedel- Crafts catalysts, activated clays, silica-alumina, copperpyrophosphate, etc., may be used. Suitable conditions when employingphosphoric acid catalysts of the U. 0. P. type are temperatures of 300F. to 500 F., pressures from 250 to 5,000 p. s. i. and feed stockscomprising refinery streams containing propylene and mixed butylenes.Suitable feed stocks, for example, may contain from to 60 mol percentpropylenes, from 0.5 to 15 mol percent butylenes, and from 0.1 to 10 molpercent isobutylene, the remaining being saturated hydrocarbons. Othersuitable feed stocks are the dimer and trimer of isobutylene.

The prefenred Ox'o alcohols employed in forming the formals of thisinvention are those having from 8 to carbon atoms derived from olefincopolymers having from 7 to 19 carbon atoms. In preparing these Oxoalcohols the desired olefin fraction is segregated from the crude olefinpolymer product by fractionation.

The following table, for example, shows the structure and percentcomposition of Ca OX0 alcohols prepared from a. C7 olefin stream whichhad been fractionated from the products obtained by the phosphoric acidpolymerization of refinery gas streams containing propylene and mixednand isobutylenes.

As was stated above, the formals of this invention, hereinafter referredto as complex form'als, may be considered to have the following generalformula:

In the formula A and B represent radicals derived from organic compoundsby removal of one reacting h'y'droxyl group. In the formula x and n are2 or more and y is one or more. The radicals represented by A and -B maybe alike or different and may contain fromxl to 60' carbon atoms. Thesum of the carbon atoms in -the molecule should be between 20 and 130and .pre'ferablyzbetween about and 100. 1.

The grou of organic compounds that satisfy th'eeonditions of the abovegeneric formula and that are used to build the preferred compoundsaccording to the concept of this invention are monohydric alcohols,glycols, and organic acids. These compounds may be advantageouslycombined with formaldehyde to form molecules having the following typeformulas, words instead of structures being given to show the componentsof the complex formals.

Alcohol-(formaldehyde-glycol Glycol- (formaldehyde-glycol a:

Glycol monoester-(formaldehyde-glycol)a Glycolmonoeth'e'r-(formaldehyde-glycol)m In all formulas given above xrepresents a Whole number greater than 11. The acids which may be usedto prepare the glycol monoesters may be selected from the followingpartial list:

Acetic Methoxy propiouic Propioni'c Ethoxyethox acetic Butyric vMono-Z-ethyl exyl adipate 2-ethyl bu'tyi-ic Mono-Cs 0 x0 sebacicCaproi'c Ca C2o 0x0 acids, including bottoms acids 2-ethylhexanoic Ac dsderived from petroleum fractions Caprylic by oxidation Pelargoni'c Acidsderived from alcohols and/or alde- Capric hydes by caustic fusion LaurieNaphthenic acids Myristlc Glycolic acid Oleic Lactic acid StearicHydroxystearic acid This concept of the instant invention may beillustrated as follows:

EXAMPLE I of n-butyl Carbitol-(CHzO-tripropylene glycol); i. e.

n-ctin ocrncHz)2ocuzocsneocansocgneonn The hemiformal of n-butylCarbitol was made by heating 81.1 g. /z mole) of the Carbitol with 15.1g. /2 mole CH2O) of paraformaldehyde, 200 g. of heptane and 2 g. ofNaHSO4 at 65 C. for half an hour.

The polyforrnal of tripropylene glycol, i. e.

was made by refluxing 384.5 g. (2 moles) of tripropylene glycol, 45.5 g.(1.5 moles CHzO) of paraformaldehyde, 200 g. of heptane and 3.2 g. ofNaHSO4 for minutes at 89 to 104? C. The volume of the water layer was 28cc. (theoretical is 27 cc.). To minimize simple formal formation'the'hemiformal of n-butyl Carbitol was added dropwise over a period of 70minutes to the refluxing solution of the polyformal of tripropyleneglycol. After the hemiformal was added refluxing at 102 C. was continuedfor an additional 30 minutes. The volume of the water layer was now 37cc. (theoretical is 36 cc.). The catalyst was removed by decanting. Themixture was then washed with three 100 cc. portions of 5% NazCOa and two100 cc. portions of water. After stripping -off the solvent andunreacted material, the product boiling above 140 C. at .2 mm. (kettletemperature of 231 C.) gave the following inspections:

Viscosity, cs. at F.:

Preparation 210 n. 50.86 (235 SUS) 100 423.1

0 -1"; 59,700 Viscosity index p Pour point, F '25 Hydrogen combustiontest: Carbon, 1.1 mgs; varnish, 0.7 mg.

' EXAMPLE II Preparation of polyethylene glycol pol'yfo'rinal i. e.,

I HO (CH2CH2O) 6.4 [CH2(OCH2CH2 GI-tOIIZrH This olyfor mal was made byheating 300g. (1 Thole) of polyethylene glycol of a molecular weight ofabout 300, 30 g. ("l-mole onto ofparaforma'ldehyde, 200 g.

Polyethylene Polytorrnal of Glycol 300 PE G-300 Viscosity, Cs. at F.:

210 5.68 (44.79 SUS) 36.40 (170.7 BUS).

'. 34.24 (159.8 SUS) 290.7 (1343 SUS).

116 132. +30. Flash Point, F 400 360. Fire Point, F 445 460Alcohol-Z-formaldehyde-alcohol Alcohol-Z-formaldehyde-glycol monoesterAlcohol-Z-formaldehyde-glycol monoether Glycolmonoester-Z-formaldehyde-glycol monoester Glycolmonoester-Z-formaldehyde-glycol monoether Glycolmonoether-Z-formaldehyde-glycol monoether By substituting a hydroxy acidmonoester such as lactates and glycolates, another series of compoundsmay be prepared as follows:

Hyd'roxy monoester-Z-formaldehyde-hydroxy monoester Hydroxymonoester-Z-formaldehyde-alcohol Hydroxymonoester-Z-formaldehy-de-glycol monoether Hydroxymonoester-Z-formaldehyde-glycol monoester It will be seen that the abovementioned complex formals all are included under the generic formula:

wherein A and B may be the same or diiferent and are selected from thegroup consisting of organic radicals containing from 1 to 60 carbonatoms which corresponds to organic compounds containing a hydroxyl groupthat is alcoholic in nature and wherein x and n are whole numbersgreater than 1 and y is 1 or more.

This concept of the invention may be further illustrated by thefollowing examples:

EXAMPLE III Preparation of C13 Oxo Alcohol-(CHzO-TripropyleneGlycol)3CI-I zO--C1z Oxo Alcohol i. e.,

C13H27O [CH2O (CaHeO 3] 3CH2-OC13H2'1 The central portion, i. e.,

H OCaHs) OCH2 OCsHe) s-OCHz OCsHs) 30H of this polyformal was first madeby refluxing 288 g. (1.5 moles) of tripropylene glycol, 30 g. (1 moleCHzO) of trioxymethylene 300 g. of heptane and 5.5 g. of catalyst(NaHSO4) for 40 minutes at 89 C. to 100 C. The volume of water collectedwas 19 cc. (theoretical is 18 00.). The reaction mixture was cooled to70 C. at which point 200 g. (1 mole) of C13 Oxo alcohol and 30 g. (1mole CHaO) of trioxymethylene were added. The reaction mixture was thenheated at reflux temperature 90103 C. for 30 minutes during which time19.5 cc. (theory is 18 cc.) of water was collected.

. The reaction product was decanted from the catalyst and then washedwith 150 cc. of NazCOa solution and finally with two 100 cc. portions ofwater. The material was then stripped free of the solvent and lightends. The material boiling above 152 C. at 0.3 mm. pressure andconsisting of the 14100% fraction had the following proper-ties:

Viscosity, cs. at F.:

0 4657 Viscosity index 132 Pour point, F. -45 Flash point, F. 420 Firepoint, F. 455

Hydrogen combustion test: Carbon, 1.3 mg.; varnish,

The clean burning characteristics of this reaction prodnot indicate thatit would give essentially no octane requirement increase if it were usedas an automotive crankcase lubricant.

EXAMPLE IV Preparation of C13 Oxo Alcohol-(CHzO-TripropyleneGlycol)2-CH2O-C1a Oxo Alcohol This complex formal which is similar tothat prepared above was made to obtain a lower viscosity material. TheC13 0x0 alcohol (520 g., 2.6 moles), 117 g. of paraformaldehyde (3.9moles CHzO), 200 g. of heptane and 3.1 g. (0.25% of NaHSO4 catalyst wereheated to 55 C. for 45 minutes. To this hemiformal of C13 Oxo alcoholwas then added 500 g. (2.6 moles) of tripropylene glycol and the mixtureheated to reflux. After three hours the temperature had risen from C. to118 C. and 73 cc. of water had been collected. (The theoretical amountof water is 70.2 cc.) The material was light tan in color indicatingthat the small catalyst concentration (0.25 was helpful in not causingexcessive discoloration which occurs when the usual 1% catalyst isemployed. The reaction product was separated from the crystallinecatalyst and washed with three cc. portions of saturated Na2CO3 solutionand then with three 100 cc. portions of water before stripping of theheptane and small amount of water. The product boiling above 153 C. at0.2 mm. mercury pressure and consisting of the 6 to 100% fraction hadthe following properties.

Viscosity, cs. at F.

210 5.82 100 33.82 0 2286 -40 80,000+ Viscosity index Pour pount, F. 50Flash point, F. 390 Fire point, F. 430

Hydrogen combustion test: Carbon, 0.8 mg; varnish,

EXAMPLEV Preparation of n-Butyl- (OCaHs 2O CHzO-Polypropylene Glycol2--CH2O( OCaHe) 2 n-Butyl The preparation of this complex formal wasaccomplished according to the description of Example IV.

The material obtained boiling above 161 C. at 0.3 mm. had the followingproperties:

Fire point, F. 345

:9 The fraction of thekprod ct boiling above .1 88 C. at 0.2 mm. had thefollowing properties:

Viscosity at 210 F. 5.39 100 F. 29.46 0 1709 40' F. 55,849 Viscosityindex 129 Pour point, F. 60 Flash point, F. 350 Fire point, F. 390

EXAMPLE VI Preparation of C13 Oxo .Alcohol-'(CHzO-TripropyleneGlycol)2.3-CH2OC1s 0x0 Alcohol Two moles C13 Oxo alcohol, 3.7 moles offormaldehyde, as paraformaldehyde, and 2.3 moles of tripropylene glycolwere admixed with 300 g. heptane rand 1.5 g. of sodium acid sulfur. Themixture was heated to reflux temperature until the theoretical water wasevolved. The product was then decanted from the catalyst and washed with100 cc. portions of sodium carbonate three times; it was then washedtwice with 100 cc. portions of water and then "filtered. The materialwas then stripped to 176 C. vapor temperature at 10 mm. The product hadthe following properties:

Viscosity at 210 .F. .8.06 (52.6'SUS) 100 F. 47.81(22l.3SUS) A 0 3491-40 F. 110,000+ Viscosity index 136 Pour point, F. -50 Flash point, F.425 Fire point, F 460 EXAMPLE VII Preparation of C13 OxoAlcohol-CH2O(Triethylene Glycol-CHzO') 2C13 Oxo Alcohol 400 g. of C13Oxo alcohol .and 6.7 .2 g. of formaldehyde was admixed and heated with2.4 g. of NaHSOq. in the presence of 240 g. of 'heptane. The mixture wasthen heated to 55 F. for approximately 25 minutes. To this mixture 300g. of triethylene glycol was added and this mixture heated to 113 C. forapproximately one hour. At this point 33.6 g. additional formaldehydewas added to the reacting mixture. This mixture was then heated to 115C. for an additional hour. At the end of this period 60 g. of water hadbeen removed (54 g. theoretical).

This product was purified in the manner similar to that of Example VIabove and stripped to 210 C. vapor temperature at 9.0 mm. pressure.

This product had the following properties:

Viscosity at EXAMPLE VIII Preparation of C13 OxoAlcohol0(CH2O-Pentanedioll,5)3CH2-O-C13 Oxo Alcohol This product wasprepared as described in Example VII above except that the glycol waspentanediol-1,5 instead of triethylene glycol. The product was strippedto a vapor temperature of 182 C. at 10 mm. pressure.

The properties of this product are as follows:

Viscosity at 210 F 2.28(67.4 SUS) F .'75.56'(349i3"SUS) 0 4,035 40 F -Q;

Viscosity index 143 Pour point, F ---35 Flash point, F 440 Fire point, F-1485 The complex formals as describedherein may serve as the lubricantbase for grease compositions. These syntheticlubricants may be thickenedto stable grease structures with conventional grease forming soaps suchas lithium soaps of high molecular weightsubstantially saturated fattyacid, the n-acyl p am'ino phenols, silica gels, treated bentinites andthe like. Oxidation inhibitors, rust inhibitors, tackiness agents andother grease addition agents may be added to the complex formal greases.The soap complexes known to the artmade by using low molecular weightacid salts .may also be used in preparing these grease compositions. .Ifdesired the complex formals of this invention may be blended withmineral oil or other synthetic lubricants such as simple bis-formals,complex esters, di-esters, phosphates, siloxanes, silicates,phosphonates and the like and a grease composition which incorporatesthe desirable characteristics of the blends may be prepared byconventional techniques.

The following illustrates the procedures used in preparing the greasecompositions generally described above:

Formulation Preparation A very good dispersion of the soap in thesynthetic oil was obtained by heating the soap and oil to 450 F. withstirring. During the early stages of heating the mass swelled. Thephenyl a'lpha-naphthylamine was added and the mass was pan cooled. Theresulting product had an excellent grease structure and had a droppingpoint of 379 F.

To summarize briefly, this invention relates to new compositions ofmatter which have outstanding utility as synthetic lubricatingcompositions. The materials contemplated may be broadly described asbeing complex formals of organic materials containing at least onehydroxyl group that is alcoholic in nature. By complex formal is meantmaterials containing more than 2 formal linkages. The structure of theformals of invention may be described as one corresponding to theformula:

where x and n are whole numbers greater than 1 and y has a value of 1 ormore. In this formula A and B are organic radicals containing from 1 to60 carbon atoms which are derived from organic materials containing atleast one hydroxyl group that is alcoholic in nature. A and B may bealike or different and the total number of carbon atoms in the moleculeshould be between about 20 and 130, preferably between about 25 and 100.The compounds that are especially preferred and that are considered tobe the preferred embodiment of this invention are those materials thathave a kinematic viscosity at 210 F. within the range of from 2 to 60centistokes, an ASTM pour point of at least as low as 35 F., and a flashpoint of at least 300 F.

The formals of this invention are useful as plasticizers,

solubilizers, grease bases, insecticides, weed killers, rustpreventives, solvents, .dewaxing aids, detergents, and as raw materialsfor many other industrial applications, such as household -detergents,fumigants, etc. These new synthetic lubricating oils may be admixed withother lubricating oils, naturally occurring or synthetic, either asconcentratesor as finished blends. They are compatible and may bevblended with the well known lubricant addition agents such as viscosityindex improvers, pour point depressors, detergents, rust inhibitors,antioxidants, and the like.

What is claimed is:

1. As a synthetic lubricant, a complex formal having an ASTM pour pointbelow about 35 F., a flash point above about 300 F., and a kinematicviscosity at 210 F. within the range of from 2 to 60 centistokes, saidformal corresponding to the formula wherein A and B are selected fromthe group consisting of hydrocarbon and substituted hydrocarbon radicalscontaining from 1 to 60 carbon atoms wherein at and n are integershaving a value of at least 2 and y is an integer having a value of atleast 1, the total number of carbon atoms in the molecule being betweenand 130.

2. A synthetic lubricant according to claim 1 wherein A is derived frommonohydric alcohol and wherein B is derived from a glycol.

3. A synthetic lubricant according to claim 1 wherein A and B areorganic radicals derived from Ca to C20 branched chain alcohols andwherein n, y and x are 3.

4. As a synthetic lubricant, a complex formal having the formula whereinA and B are organic radicals derived from C8 to C20 alcohols and whereinx and n are numbers having the value of 2 or more and y is an integerhaving a value of at least 1, said formal being formed by reactingtogether x.y moles of a glycol with x-I-l moles of formaldehyde and 2moles of an alcohol containing from 8 to 20 carbon atoms, said formalhaving an ASTM pour point below about +35 F., a flash point above about300 F., and a viscosity at 210 F. within the range of from 2 to 60centistokes, the total number of carbon atoms in the molecule beingbetween about to 100.

5. A synthetic lubricant according to claim 4 wherein said alcohol isahighly branched chain aliphatic alcohol of 8 to 20 carbonatoms.

6. A synthetic lubricant according to claim 4 wherein said glycol istripropylene glycol.

7. A synthetic lubricant according to claim 4 wherein said glycol is apolyethylene glycol.

8. A synthetic lubricant according to claim 4 wherein said alcohol is ahighly branchedchain aliphatic alcohol of 13 carbon atoms alcohol andwherein x, n, and y are 3.

9. A synthetic lubricant according to claim 4 wherein said alcohol is anether alcohol, wherein said glycol is a polypropylene glycol of amolecular weight of about 150 and wherein x is 2.

10. A synthetic lubricant according to claim 4 having an ASTM pour pointof below l5 F., a flash point in excess of 350 F. and viscosity at 210F. of from 2.6 to 13.0 centistokes.

11. As a synthetic lubricant, a complex formal of the formula wherein Aand B are selected from the group consisting of hydrocarbon andsubstituted hydrocarbon radicals containing from 1 to carbon atoms andwherein x and n are numbers having the value of at least 2 and wherein yis a number of at least 1 thickened to a grease consistency with alithium soap of a high molecular weight fatty acid, said complex formalhaving an ASTM pour point below about +35 F., a flash point above about300 F., and a viscosity at 210 F. within the range of from 260centistokes, the total number of carbon atoms in said formal beingbetween about 20 to 130.

References Cited in the file of this patent UNITED STATES PATENTS2,350,350 Gresham June 6, 1944 2,379,703 Geltner July 3, 1945 2,397,602Gresham Apr. 2, 1946 2,436,347 Zimmer et al Feb. 17, 1948 2,473,994Gresham June 21, 1949 2,594,341 Owen et al. Apr. 29, 1952 OTHERREFERENCES Wender and Orchin: Critical Review of Chem. of 0x0-Synthesis, Bur. of Mines, R. I. 4270, June 1948, pages 6 and 9.

1. AS A SYNTHETIC LUBRICANT, A COMPLEX HAVING AN ASTM POUR POINT BELOWABOUT 35*., A FLESH POINT ABOVE ABOUT 300* F., AND A KINEMATIC VISCOSITYAT 210* F. WITHIN THE RANGE OF FROM 2 TO 60 CENTISTOKES, SAID FORMALCORRESPONDING TO THE FORMULA
 11. AS A SYNTHETIC LUBRICANT, A COMPLEXFORMAL OF THE FORMULA